Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J195/00—Adhesives based on bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

• the present invention relates to self-adhesive bituminous compositions modified with polymers and generally used for manufacturing watertight roofing shingles. More particularly, the present invention relates to bituminous self-adhesive compositions having improved properties particularly advantageous for cold applications and offering rapid adhesion, resistance to peeling, and desirable ring-and-ball temperature (RBT).
• RBT ring-and-ball temperature
• the present invention involves watertight shingles having at least one layer of the inventive bituminous composition which composition utilizes bitumen, polymers, and mineral loads.
• bituminous compositions disclosed herein can also contain mineral or synthetic fibres and thixotropic agents such as silica.
• bituminous compositions for manufacturing watertight shingles generally for roof covering.
• Traditional systems for making these products involve a process of warming up bitumen or flame soldering. It is obvious that this type of technique is dangerous considering the risk of fire caused by the utilization of a torch and other similar equipment.
• Self-adhesive compositions comprising one linear styrene-butadiene-styrene tri-block copolymer and styrene-butadiene di-block copolymer are also known; however, these compositions require the use of mineral oil during application, and their properties are not acceptable from RBT and flow resistance points of view. The presence of oil can also increase the exudation risk.
• a bituminous self-adhesive cold-application composition responding to the criteria mentioned above is then the object of the present invention.
• the present invention provides a bituminous self-adhesive cold-application composition that comprises a mixture of bitumen, a mixture of different thermoplastic polymers and tackifying resins, mineral loads, and optionally, fibres and/or thixotropic agents.
• the present invention also teaches watertight roofing panels having at least one bituminous self-adhesive cold-application layer of the inventive composition.
• the present invention also discloses a process for manufacturing the watertight panels.
• the bituminous composition of this invention may also contain the usual mineral loads, including mineral or synthetic fibres, as well as thixotropic agents. These loads are generally used at the rate of about 0 to 40%, based on the weight of the bituminous composition.
• bituminous self-adhesive cold-application composition meets not only all required properties from the point of view of cold adhesion, obsolescence, ring-and-ball temperature and cold elasticity, but also that the properties of the composition remain satisfactory even when one or more polymers are added. Furthermore, generally improved properties are obtained when at least three polymers are present.
• the bituminous composition of the invention comprises, in addition to tackifying resins and bitumen that will be described later, a mixture of different polymers selected from (A), (B) and (C) described in detail below:
• the copolymer (A) preferably represents between 10 and 45 weight percent of the total polymeric mixture and more preferably between 15 and 35 weight percent of the polymeric mixture.
• the copolymer (B) preferably represents between 5 and 50 weight percent of the polymeric mixture and more preferably between 5 and 25 weight percent of the polymeric mixture.
• (C) Styrene-diene di-block copolymer preferably styrene-butadiene in which the styrene portion represents from about 15 to 45 weight percent and preferably from about 20 to 35 weight percent and whose total molecular weight is between 50,000 and 150,000, and preferably between 50,000 and 100,000.
• copolymer (C) used in the present invention is of the type utilizing statistical interlinking which means that it contains one styrene block and one styrene-butadiene block in a statistical distribution. Generally, the styrene block represents about 70% of the total styrene.
• Copolymer (C) is used simultaneously as a compatibility agent and an adhesive.
• Copolymer (C) preferably represents approximately 10 to 75 weight percent of the polymeric mixture and more preferably from 30 to 60 weight percent.
• Styrene-conjugated diene block copolymers appropriate for the present invention also include their partially and totally hydrogenated derivatives.
• the bituminous composition of the invention may also contain one or more tackifying resins at the rate of from about 0 to about 25 weight percent of the total bituminous composition. Higher quantities can be used but to the detriment of some properties.
• the role of tackifying resins is well known in the sector of adhesives.
• tackifying resins are well known conventionally and are more particularly described in U.S. Pat. No. 4,738,884, which is incorporated herein by reference in its entirety.
• bitumen useful in the present invention can be direct distillation bitumen or oxidized bitumen, natural bitumen, precipitation bitumen and others. It is also clear that different types of bitumen can be mixed as well as modified by addition of one or more oils.
• bitumen having a penetration index at 25° C. of less than 800 (0.1 mm) (ASTM D 5-73 norm), and preferably between 30 and 400.
• Direct distillation bitumen is preferable, with a preference for one which has a penetration index between 80 and 250.
• the block copolymers (A), (B) and (C) are well known in the polymer field. They are generally obtained during anionic polymerization of monomer feeds in a solvent in the presence of an alkylmetallic catalyst such as alkyllithium. They can be prepared during successive polymerization of styrene and butadiene or isoprene when linear block copolymers are involved. In case radial structure block copolymers are involved, copolymers able to exhibit at least three branches are utilized, with every branch having at least one polystyrene block and one polybutadiene or polyisoprene block. This method is described in U.S. Pat. No. 3,281,383, which is incorporated by reference herein in its entirety.
• copolymers can comprise statistical parts and be within the scope of the present invention. Copolymers do not have to be necessarily of a symmetric composition. All molecular weights referred to in this disclosure are weight-average molecular weights (M w ).
• the present invention also discloses watertight roofing panels which comprise at least one cold-application self-adhesive layer made according to the above described bituminous composition and one or more optional bituminous layers modified with polymers and possibly with added mineral loads.
• inventive compositions can constitute the entire watertight panelling, even though it was necessary to use other layers in conventional roofing compositions to guarantee required thermo-mechanical properties (e.g. RBT) and for providing a non-adhesive layer comprising bitumen modified with a rubbery polymer, and mineral loads and other thixotropic agents.
• the present invention eliminates this need for additional non-adhesive layers of bitumen, rubbery polymer modified bitumen, and bitumen loaded with minerals and thixotropic agents.
• compositions of the present invention present a great advantage over conventional techniques since they not only exhibit improved properties but can also be used in the form of sole composition sheets.
• bituminous self-adhesive cold-application compositions of the present invention can also be used for other purposes such as mastics, emulsions or other watertight sealants.
• compositions were prepared with a laboratory mixer having a high coefficient of shearing (SILVERSON type). Staple bitumen was heated to a temperature of 180° C. in a thermostatic-controlled oil bath. Different rubbery components were introduced into the bitumen together with one or more tackifying resins. Introduction of the tackifying resins after complete dispersion of the rubber was also tested but it apparently had no observable influence on the results. Dynamic viscosity was measured with a rotational conical and planar system from HAAKE company. The indicated viscosity corresponds to a coefficient of shearing of 100 s-1.
• bituminous composition was dissolved in an equal quantity of toluene to obtain a paste of good consistency which was applied with a scraper to a polyester film, with a constant thickness of the paste.
• This film had previously been treated with toluene to remove the fat content.
• toluene was evaporated in an oven at 50° C. for 1 hour. The result was a polyester film covered with a homogeneous layer of constant thickness (30 microns) of the bituminous composition.
• This method of preparation of samples for the peeling test is very important because it guarantees good uniformity and constant thickness of bituminous composition as well as a constant application force.
• Dynamic Elongation factor PEN at 25° C. viscosity to breaking Cold folding* (ASTM D 5-65) at 180° C. (ASTM D-412) (DIN 52123) Ex. (0.1 mm) (m Pa.s) (%) (° C.)
• NYNAS B 200 is a commercially available bitumen having a penetration index of around 200, and is manufactured by NYNAS Company.
• the RBT vales, Peeling resistance and Tack values of the examples above exceed the values which can be obtained from conventional adhesives such as hydrocarbure types and resin derivatives.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Civil Engineering (AREA)
• Structural Engineering (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Sealing Material Composition (AREA)

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Citations (11)

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• 1993
  • 1993-03-24 BE BE9300288A patent/BE1006890A3/fr not_active IP Right Cessation
• 1994
  • 1994-03-17 US US08/210,217 patent/US6172145B1/en not_active Expired - Fee Related
  • 1994-03-23 DE DE69420765T patent/DE69420765T2/de not_active Expired - Fee Related
  • 1994-03-23 ES ES94870050T patent/ES2137346T3/es not_active Expired - Lifetime
  • 1994-03-23 AT AT94870050T patent/ATE184903T1/de not_active IP Right Cessation
  • 1994-03-23 EP EP94870050A patent/EP0617104B1/de not_active Expired - Lifetime
  • 1994-03-23 DK DK94870050T patent/DK0617104T3/da active
• 1999
  • 1999-12-17 GR GR990403278T patent/GR3032192T3/el unknown
• 2000
  • 2000-09-18 US US09/664,217 patent/US6538053B1/en not_active Expired - Fee Related

Patent Citations (11)

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